Process of producing a chalcopyrite semiconductor film

Abstract: A I-III-VI ₂ chalcopyrite semiconductor film containing a Group VII element as a dopant, and methods to produce such a chalcopyrite film are provided. The chalcopyrite film of the present invention has stoichiometric composition, and electrical characteristics such as p-n conduction type, carrier concentration and the like are controlled.

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a process for the production of a chalcopyrite structure semiconductor thin film containing a specific dopant. Description of the Related Art The chalcopyrite structure semiconductor is a material useful for constituting light-emitting devices and solar cells, because its forbidden band can be wide from a visual region to an infrared ray region and it has a large optical absorption coefficient due to the constituent elements. It is indispensable to produce a p-n junction in manufacturing the solar cells or light-emitting devices. For controlling a p-n conduction type of the chalcopyrite thin film, a method of changing the composition ratio between a Group I element and a Group III element or between a Group II element and a Group IV element which are the constituent elements of chalcopyrite compounds has been used conventionally. For example, in the case of CuInSe 2 thin film, the n-type is formed when the proportion of the Group I element Cu is less than that of the Group III element In, and in the opposite case the p-type is formed. In these cases, a problem is encountered in that many lattice defects occur due to deviations in the composition ratio. There are also such problems as depositions of excessive amounts of components or the appearance of an impurity phase other than the chalcopyrite structure. R. Noufi et al., also report that it is difficult to control the carrier concentration and resistivity by changing the composition ratio (Appl. Phys. Lett., 45 (1984) p.688). Particularly, most of the chalcopyrite semiconductor thin films which go in the direction of the n-type by deviation in the composition ratio show a high resistance, and thus a low resistance film is not obtainable. In fabricating the p-n junction by using the chalcopyrite thin film produced by the prior art, such inconveniences as the lattice defects and depositions of excessive amounts of components owing to deviations of composition ratio, or the impurity phase other than the chalcopyrite-structure appear as mentioned before. Thereby, electrical and optical characteristics of the chalcopyrite thin film are deteriorated. Thus, when the devices having the p-n junction are manufactured by using the chalcopyrite thin film produced by the prior art, efficiency of the devices are inferior due to the deterioration of electrical and optical characteristics. For example, by increase of carrier recoupling centers due to the lattice defects and the impurity phase, the open-circuit voltage of the solar cell drops and also the quantum efficiency of semiconductor laser drops. When an n-type high resistance film is used, in the solar cells the short-circuit current decreases, and in the light-emitting devices the carrier injection efficiency reduces. Thus, the conversion efficiency of the solar cells and the luminous efficiency of the light-emitting devices are deteriorated. Moreover, in the solar cells, the depletion layer of the p-n junction must be broadened to convert incident light efficiently into electrical energy. Thus it is necessary to control the carrier concentration. US-A-4 004 342 concerns a method of manufacturing lightemitters and photovolteic detectors by implanting bromine or chlorine ions into a p-type CuInSe 2 substrate so as to form a p-n junction. SUMMARY OF THE INVENTION The present invention provides a process of producing a chalcopyrite structure semiconductor film comprising a Group I-III-VI 2 chalcopyrite compound containing a Group VII element as a dopant. The present invention further relates to a process of producing a chalcopyrite thin film, whereby conventional problems are solved, constituent element composition is in a stoichiometric ratio and electrical characteristics such as p-n conduction types and carrier concentration are controlled. The process of producing the chalcopyrite structure semiconductor film of the present invention comprises: depositing a I-III-VI 2 chalcopyrite compound film on a substrate while evaporating onto the substrate a Group VII element, to obtain a I-III-VI 2 chalcopyrite compound film containing the Group VII element therein as a dopant. In a preferred embodiment, the process further comprises the step of heat treating the chalcopyrite compound film containing the Group VII element as a dopant, preferably in an atmosphere containing gas selected from the group consisting of hydrogen, nitrogen, oxygen, helium and argon. The preferable temperature of the heat treating lies in the range of from 200°C to 400°C. In another preferred embodiment, the process further comprises the step of heat treating the chalcopyrite compound film containing the Group VII element as a dopant in an atmosphere containing a vapor of the Group VI element. BRIEF DESCRIPTION OF THE DRAWINGS FIG.1 is a longitudinal sectional view showing a schematic configuration of an apparatus for obtaining a I-III-VI 2 chalcopyrite structure semiconductor thin film doped with a Group VII element according to one embodiment of the present invention. FIG.2 shows the relationship between a substrate temperature, a InCl 3 crucible temperature and resistivity of a CIS:Cl film obtained according to embodiment 1 of the present invention. FIG. 3 shows, among others, the distribution of the Cl element in a CIS:Cl film obtained in embodiment 1 as curve a.). FIG. 4 is a longitudinal sectional view showing an example of configuration of a light-emitting device using a I-III-VI 2 film produced according to the process of the present invention. DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method for the production of a Group I-III-VI 2 chalcopyrite structure semiconductor film containing a Group VII element as a dopant. In the I-III-VI 2 chalcopyrite structure semiconductor thin film produced according to the process of the present invention and containing the Group VII element as a dopant, the composition of constituent elements is in a stoichiometric ratio, and electrical characteristics such as p-n conduction types and carrier concentration are controlled. According to the production process of the present invention, by simultaneously evaporating the Group VII element onto the substrate during depositing the Group I-III-VI 2 chalcopyrite structure semiconductor thin film on the substrate by evaporation, sputtering or the like, the Group VI element in the deposited chalcopyrite structure is partly substituted by the Group VII element. As mentioned above, the I-III-VI 2 chalcopyrite structure semiconductor thin film obtained by the present invention becomes a semiconductor film showing an n-type conduction in the presence of excessive electrons caused by partial substitution of the Group VI element by the Group VII element. The ratio of the element (dopant) substituted partly as aforementioned against the main element is very small, usually 0.1 atomic % or less, and therefore, the composition ratio of the resultant chalcopyrite thin film can be kept in a stoichiometric ratio. Thus, there is no appearance of lattice defects and excessive component depositions due to the deviation of the composition ratio nor appearance of an impurity phase other than the chalcopyrite structure. Also, in such a production process, by controlling the evaporating velocity of the Group VII element as the dopant, the carrier concentration or resistivity of the resultant film can be controlled. Thus, the degree of freedom on designing the solar cells or light-emitting devices increases, and the desired carrier concentrations or the like necessary for the devices can be obtained easily. The Group I element which is applicable to the process of the present invention is, for instance, Cu or Ag. The Group III element which is applicable to the process of the present invention is, for instance, Al, Ga or In. The Group VI element which is applicable to the process of the present invention is, for instance, S, Se or Te. The Group VII element which is applicable to the process of the present invention is, for instance, F, Cl or Br. In the following, the embodiments of the present invention are described with reference to the drawings. Embodiment 1 FIG.1 shows a schematic configuration of an apparatus for obtaining a chalcopyrite structure semiconductor thin film. In a vacuum container 1, a support 4 is disposed holding a substrate 2 for depositing a chalcopyrite thin film thereon and including heater 3 for heating the substrate 2. Moreover, in the container 1, a source 5 of Cu, a source 6 of In and a source 7 of Se, which are main constituent elements of chalcopyrite compound CuInSe 2 , and a source 8 of a dopant including InCl 3 are provided. An opening 9 is connected to an exhaust system. Source crucibles of Cu, In and Se were heated in vacuum of about 1.33 10 -5 Pa (10 -7 Torr) respectively at 1140°C, 860°C and 200°C to evaporate the elements, and simultaneously, Cl was evaporated from the source of InCl 3 to deposit a CuInSe 2 :Cl (CIS:Cl) film on the substrate. Hereinafter, this production process is referred to as "simultaneous evaporating process". Hereupon, when InCl 3 is heated, InCl 3 is decomposed and only Cl is evaporated at the temperature of about 300°C or less. A glass plate partly covered by a ZnO film or an Au film was used as the substrate. FIG.2 shows the relationship between the substrate temperature during film forming, InCl 3 crucible temperature and resistivity of the resultant CIS:Cl film. Hereupon, the higher the InCl 3 crucible temperature is, the faster is the evaporating velocity of Cl or the greater the deposition quantity to the substrate. The composition ratio Cu/In of the resultant film is within a range of from 0.95 to 1.00, and Se/(Cu +In) is within a range of from 1 to 1.02, and thus a stoichiometric composition ratio (Cu:In:Se = 1:1:2) is substantially satisfied. All of the resultant films were of the n-type. When forming the film at the substrate temperature of 500°C, regardless of the InCl 3 crucible temperature, the resistivity of the resultant film was 10 4 Ωcm or more. Since the resistivity of a CuInSe 2 (CIS) film of stoichiometric composition ratio without Cl is about 10 5 to 10 4 Ωcm, when forming the film at the substrate temperature of 500°C it is understood that Cl hardly goes into the film. When forming the film at the substrate temperature of 400°C, the film resistivity drops to 10 3 Ω cm when the InCl 3 crucible temperature is kept at 300°C. On the contrary, when forming the film at the substrate temperature of 300°C, the film resistivity drops abruptly as the InCl 3 crucible temperature rises. From the above facts, it is understood that Cl is effectively taken into the film at the substrate temperature of about 300°C during film forming. When forming the film at the substrate temperature of 300°C, the film resistivity or the carrier concentration can be controlled by the InCl 3 crucible temperature. However, as a result of X-ray diffraction, it is understood, that, when forming the film on the glass and the Au film, the CIS:Cl film produced at the substrate temperature of 400°C or higher forms a chalcopyrite structure, while the film produced at the substrate temperature of 300°C does not form the chalcopyrite structure. Thus, this process is not suitable for forming the film on amorphous substrates such as glass plates and metal films. However, similarly from an X-ray diffraction pattern, it is confirmed that the chalcopyrite structure is formed not only in the case of a substrate temperature of 400°C or higher, but even in the case of a substrate temperature of 300°C, when forming the film on a ZnO film. Thus, the reliability of this production process is dependent on the substrate being used, and therefore, this point should be noted. The preferable substrate is of a material having polycrystal structure, and amorphous materials or metals are not suitable. A semiconductor of a Group IV, e.g., Si, a Group II-VI compound, e.g., CdS or an oxide, e.g., ITO (indium tin oxide), SnO 2 or Al 2 O 3 is suitable for the substrate. FIG.3 shows results of testing distributions of Cl elements in the CIS:Cl film produced in the aforementioned embodiment by a secondary ion mass analysis. A curve "a" shows the Cl distribution of the CIS:Cl film produced by the simultaneous evaporating process. The results shown are tested on the films produced at the substrate temperature of 300°C and the InCl 3 crucible temperature of 250°C for the simultaneous evaporating process. It is understood that, in the simultaneous evaporating process Cl is distributed equally in the film. Embodiment 2 Description will be made on the result of heating the CIS:Cl film produced by the simultaneous evaporating process in an Ar atmosphere at 400°C for 30 minutes. Hereinafter, this is referred to as "after heat treatment". The film produced at the substrate temperature of 400°C or higher shows no change in resistivity before and after the after heat treatment. On the contrary, the resistivity of the film produced at the substrate temperature of 300°C and InCl 3 crucible temperature of 200°C or higher is lower by one digit than that before the after heat treatment. The reason for this is believed that substitution takes place from dislocated Cl having entered between lattices to Se forming the crystal structure, and the amount of Cl supplying electrons has increased (increase in activation rate). Although the chalcopyrite compound film is deposited by three-source evaporation in the above-mentioned embodiment, another preferable deposition method, for example, sputtering or selenization of Cu/In layers in H 2 Se atmosphere may be employed in the process of the present invention. Additionally, the following is a brief explanation for the phrase "after heat treatment". The appropriate temperature for heat treatment is between 200 °C and 600 °C. The heat treating time even at the lowest temperature is shorter than 5 hours. As the temperature increases, the treating time becomes shorter. As stated above, such after heat treatment will effect activation of the dopant or controlled distribution of the dopant. Embodiment 3 Evaporating source crucibles containing Cu, Al, Se and CuCl were respectively heated at 1140°C, 1200°C, 200°C and 400°C; and a CuAlSe 2 :Cl film was deposited on GaAs crystals having a (100) face at the substrate temperature of 600°C. The resultant film was of the n-type and its resistivity was 1 Ωcm. Since the CuAlSe 2 film obtained without evaporating CuCl was of the p-type, it is understood that the conduction type can be controlled by doping Cl. However when this film was heat treated in an Ar atmosphere at 500°C for 3 hours, the film resistivity dropped to 10 -2 Ωcm. Embodiment 4 FIG.4 shows one embodiment of a visual range light-emitting device manufactured by using the present invention. A low resistance p-type CuAlSe 2 film 21 is formed on a GaAs substrate 20, and a high-resistance p-type CuAlSe 2 film 22 is formed thereon. Cu, Al, Se and CuCl are evaporated simultaneously on the high-resistance p-type CuAlSe 2 film 22 to form a high-resistance n-type CuAlSe 2 :Cl film 23. Then, the evaporation amount of CuCl is increased to form a low-resistance n-type CuAlSe 2 film 24. Finally, electrodes 25, 26 consisting of Al or Au are disposed. A blue light emission is obtained by injecting the carriers into the p-n junction. At this time, since the carriers are injected from the low-resistance CuAlSe 2 :Cl film 24, they can be injected efficiently. Thus, the luminous efficiency can be improved.

Claims: A process of producing a chalcopyrite semiconductor film comprising: depositing a Group I-III-VI 2 chalcopyrite compound film on a substrate while evaporating onto said substrate a Group VII element to obtain a I-III-VI 2 chalcopyrite compound film containing said Group VII element therein as a dopant. The process in accordance with claim 1 which further comprises the step of heat treating said chalcopyrite compound film. The process in accordance with claim 2 wherein said step of heat treating is carried out in an atmosphere containing at least one member selected from the group consisting of hydrogen, nitrogen, oxygen, helium and argon. The process in accordance with claim 2 wherein said step of heat treating is carried out in an atmosphere containing a vapor of the Group VI element.

Inventors: KOHIKI SHIGEMI, NEGAMI TAKAYUKI, NISHITANI MIKIHIKO, WADA TAKAHIRO, KOHIKI, SHIGEMI, NEGAMI, TAKAYUKI, NISHITANI, MIKIHIKO, WADA, TAKAHIRO
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1994
Main classification: H01L31
IPC codes: H01L31, H01L33, H01L21, H01S5